Note: Descriptions are shown in the official language in which they were submitted.
il ST~BLE ~QUEOU~; DISP~:RSION OF MIXED ~ESINS
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I! BACKGROUND OF THE INVENTIO~
li This invention relates generally to thermosetting
icoating compositions that are useful for coating substrates such
as metal surfaces.
In the manufacture of metal containers, a thin
~protective synthetic resin coating is applied to the interior
~of the container. The synthetic resins employed for coating
~ the interior of the metal container are nominally heat-curable
;~polymeric compositions which are applied in the form of a
solution or dispersion in a volatile organic solvent. During the
i drying and baking cycle of a coating operation, there is the
,jproblem of contending with the hazard of solvent vaporization
and recovery.
I' The can manufacturing industry utilizes cans which are
, fabrica~ed from aluminum or steel. The interior of the cans
i~are coated with a thin thermoset film to prevent the contact
j~of the interior metal surface of the can with its contents. I
Such coatings ideally s~ould have good adhesion to the interior
~Imetal surface, low extractables to prevent contamination of the
Icontainer contents, and a rapid cure rate for economy of
,container manufacture. Typical synthetic resin coating
,compositions include vinyls, butadienes, epoxies, alkyl/amino-
,plasts, and oleoresinous materials. Many of these resinous 1,
llcoatir,g systems ha~e the disadvantage that they require batch
,premixing just prior to a coating operation, or they require
¦Icontinuous in line mixing in a container coating assembly.
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Various technical investigations have addressed the
most serious of the problems relating to industrial scale
application of protective coatin~s to articles of manufacture.
, U.S. 3,118,848 describes coating compositions which are
prepared by mixing together a water-soluble salt of a vinyl
polymer, and a water-soluble epoxy or polyhydroxy compound.
`!One or more water-soluble phenol-aldehyde or amino resins,
notably water-soluble urea-aldehyde or melamine-~al~ehyde resins, ~,
'may optionally be included as curin~ agents ~here low baking
!temperatures are contemplated.
¦l ~.S. 3,156,740 describes thermosetting acrylic resin
compositions adapted for application as coatings to protect
metal surfaces from the action of water, soap, grease, light
,and prolonged heat. Illustrative of the preparation of a
1~ thermosetting resin composition, there are co-reacted (a) a
,copolymer of 2-10~ of acrylic acid, 4.5-88~ styrene and 9~93%
;of 2-ethylhexyl acrylate and (b) 1-epoxyethyl-3,4-epoxycyclo-
nexane, and then there is mixed therein (c) a melamine-
lformaldehyde resin in an amount of 5-S0~ by weight based on the
'total non-volatile content of the composition.
! U.S. 3,215,756 describes heat-curable mixtures of a
vinyl polymer with an epoxy compound in the presence of an
jiamino resin: For example, a methacrylic acid/methyl acrylate
;copolymer is admixed with a polyglycidyl ether of Bisphenol A
land a urea-formaldehyde resin in an organic solvent, and then
',coated on a substrate and baked to a thermoset film.
¦¦ ~J.S. 3,403,088 describes water-dispersed coating
compositions which can be applied by electrodeposition. The
coating compositions contain an at least partially neutralized
;acrylic interpolymer and an amine-~ldehyde condensation product
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¦or a polyepo~ide or both.
,1 U.`S. 3,418,392 describes a crosslinking composition for
'an interpolymer (e.g., styrene~n-butyl acrylate/methacrylamide)
Iwhich consists of a mixture of a polycycloaliphatic polye~oxide ¦ ;
(e.g., 3,4-epoxy-6-methylcyclohexylmethyl 2,4-epoxy-6-
methylcyclohexanecarboxylate) and a reactive triazine compound
(e.g., hexamethoxymethylmelamine). The coating composition is
reco~mended for use in textile print pastes, padding liquor for
llpigment dyeing of textiles, non~70ven textile impregnation
idispersions, and generally as solvent based protective coatings
lfor metal surfaces and the like.
¦ V.S. 3,467,730 describes heat-convertible coating
compositions which are prepared from carboxy-containing
'copolymers, epoxide resins and aminoplast resins. In an example,
,37 grams of a 50~ copolymer (72% styrene, 20~ methyl acrylate
and 8% acrs~lic acid) solution, 6.? grar.ls of â polyglycidyl
ether of Bisphenol A and 8.3 grams of a butylated urea-formal-
dehyde resin were blended, drawn down on glass, and cured at
200C. for 30 minutes.
I U.S. 3,908,049, describes a method for coating metal
`surfaces ~hich involves preparing an aqueous dispersion
containing a mixture of a neutralized ~ater-dispersible
Icarboxylic acid containing pol~ler, a water-dispersible heat-
¦,curable thermosetting aminoplast or polyepoxide resin and a
!!water-insoluble, long chain monohydroxy alcohol having
8-36 carbon atoms, applying the aqueous dispersion to a m~tal
j~surface, and baking the coating at 350~-450~F. to volatilize
I!the alcohol and cure the coating.
¦l U.S. 3,960,979 describes a fast curing high solids
,coating composition which can be applied to the interior of food
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and beverage cans with a hot melt spray gun. The coating com-
posit:ion is a blend of (a) a low molecular weight epoxy resin
(b) a liquid nitrogen resin or phenolic crosslinkinq agent, (c)
a flexibilizing polyol, (d) an inorganic ~r organic monomeric or
polymeric acid which acts both as reactant and catalyst, and
optionally (e) a surface modifier such as an acrylic polymer con-
taining acrylic acid.
There is continuing research effort directed to the
development of improved heat-curable resin coating systems
adapted for application as protective films on metal surfaces
and other substrates.
Accordingly, it is an object of this invention to pro-
vide an improved water-reducible heat-curable thermosetting coat-
ing composition adapted for the protective coating of metal sur-
faces.
It is another object of this invention to provide a
coating system which comprises a stable dispersion of heat-cur-
able mixed resin solids in water.
It is a further object of this invention to provide a
stable water-reducible epoxy resin dispersion adapted for one
package baked coating applications.
Other objects and advantages of the present invention
shall become apparent from the accompanying description and
examples.
DESCRIPTION OF THE I~ENTION
According to the present invention there is provided
a process for preparing a stable aqueous dispersion of mixed re-
sins comprising the steps of (1) preparing a solution of an
aminoplast in a substantially water-miscible organic solvent;
(2) heating the solution and adding thereto a mixture of vinyl
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poly:merization catalyst and ~ olefinically unsaturated carboxy-
lic acid monomer and at least one other vinyl polymerizable
mono:mer to form a polymerization product solution wherein the
unsaturated monocarboxylic acid monomer is present in the amount
of about 20 to about 90 weight percent based on total monomer
weight; (3) admixing and heating together the polymerization pro-
duct solution and an epoxy resin; (4) at least partially neutra-
lizing the admixture with ammonia or an organic amine; and
(5) dispersing the admixture into an aqueous medium to provide a
stable aqueous dispersion of mixed resin solids having a solids
content in the range of between about 15 to about 40 weight per-
cent wherein the aminoplast component is present in the amount
of about 1 to about 12 weight percent, the monomers are present
in the amount of about 20 to about 40 weight percent and the
epoxy resin component is present in the amount of about 48 to
about 79 weight percent, said weight percents being based on the
total weight of aminoplast, monomers and epoxy resin components.
In another embodiment, the present invention further
provides a process for the preparation of a stable aqueous dis-
persion of mixed resins adapted for application as a thermoset-
ting protective coating for metal surfaces, which process com-
prises the steps of (1) preparing a solution of an aminoplast
component in a substantially water-miscible organic solvent;
(2) heating and maintaining the temperature of the solution in
the range between about 120-300F., and adding to the solution
at a uniform rate over a period between about 0.5-6 hours, a
blend of a vinyl polymerization catalyst and monomers comprising
(a~ between about 20 to about 90 weight percent based on total
monomer weight of an ~, ~-olefinically unsaturated carboxylic
acid, and (b) 10 to about 80 weight percent based on total mono-
mer weight of at least one olefinically unsaturated monomer which
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is copolymerizable with the carboxylic acid monomer, thereby
forming a polymerization product solution; (3) admixing and
interacting at a temperature between about 100 to about
300F., the polymerization product solution and an epoxy
resin component, wherein said epoxy resin is a glycidyl poly-
ether of a polyhydric phenol or hydrogenated phenol and contains
an average of more than one epoxide group per molecule and
has an epoxy equivalent weight in the range between about 150
to about 8,000; (4) treating and at least partially neutralizing
the admixture reaction product medium with a basic reagent sel-
ected from ammonia and amines, thereby forming a substantially
homogeneous single phase solution; and dispersing the said
solution into a sufficient quantity of water to provide a
stable aqueous dispersion of mixed resins having a solids
content in the range between about 15 to about 40 weight
percent. The aminoplast component is present in the amount
of about 1 to about 12 weight percent, the monomers are
present in the amount of about 20 to about 40 weight percent
and the epoxy resin component is present in the amount of
about 48 to about 79 weight percent, said weight percents
being based on the total weight of aminoplast, monomers and
epoxy resin components. Sufficient organic solvent is used
to render the resin components fluid, generally about 30 to
about 85 weight based on the total weight of aminoplast,
polymerized monomers, epoxy resin and organic solvent.
In yet another aspect, the invention provides a
method for protecting the surface of an article of manufacture
which comprises applying to the surface a coating of a stable
aqueous dispersion of heat-curable mixed resins, and heat-
treating the coating to form an adherent thermoset film
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on the surface of the article, wherein the said stable aqueous
dispersion coating composition is prepared by the process here-
inbefore defined.
Aminoplast Component
The aminoplast component employed can be any of the
aldehyde condensation products of compounds such as urea, ethyl-
ene urea, dicyandiamide, various triazines, e.g., melamine,
benzoguanamine and acetoguanamine, and the like; and mixtures
and etherified derivatives of these condensation products.
Procedures for preparing aminoplasts are described
in A~inoplasts, C. P. Vale (Cleaver-Hume Press, Ltd., London).
Further illustration of aminoplast preparation and application
is set forth in United States Patents 2,957,835; 3,501,429;
3,522,159; 3,535,148; 3,773,721; 3,852,375; 3,891,590;
3,954,715; 3,965,058; 3,979,478; 4,071,578; and the like.
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The aldehyde used in preparation of the aminoplasts may
be (1) monofunctional or (2) polyfunctional, having an at least
two aldehyde groups separated by at most one carbon atom; such as
formaldehyde, paraformaldehyde, polyoxymethylene, trioxane,
lacr`olein, and aliphatic or cyclic aldehydes such as glyoxal,
,acetaldehyde, propionaldehyae, butyraldehyde, and furfuraldehyde.
~Condensation, when using formaldehyde, furfuraldehyde, paraformal-
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Idehyde, polyoxymethylene or trioxane, i5 generally accompl shed
Iwith the use of a mildly acid or mildly alkaline catalyst. When
,using acrolein, glyoxal, acetaldehyde, propionaldehyde, or butyral-,
dehyde, condensation is generally acccomplished by combining the
reactants in the presence of a strongly acid catalyst, neutralizir.g
the reaction product, adding more aldehyde, and further reacting
l;in the presence of a mildly acid, or al};aline catalyst. The
Iprefexred aldehyde is formaldehyde.
" These aldehyde condensation products (i.e., aminoplasts)
contain methylol or similar alky~ol groups, the structure of the
- alkylol group depending upon the particular aldehyde employed.
!All or part of these alkylol groups may be etherified by reaction
jwith an alcohol. Among the preferred amine-aldehyde products for
j;use in the present invention are those which are substantially
l!alkyl~ted by an etherification reaction, i.e., in which at least
¦la major portion of the alkylol groups have been reacted with an ¦
¦lalcohol. Essentially any monohydric alcohol can be employed for
this purpose, including such alcohols as methanol, ethanol, pro-
'panol, butanol, heptanol and other alkanols having up to about 12carbon atoms or more, as well as benzyl alcohol and other aromatic ¦
alcohols, cyclic alcohols such as cyclohexanol, monoethers of
,glycols such as the Cellosolves and Carbitols, and halogen-sub-
jstituted or other substituted alcohols, such as 3-chloro-pro~anol.
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When using alcohols having more than about 4 carbon
atoms, the methylol groups are first etherified with a lower
;alcohol containing 1 to 4 carbon atoms followed by ether inter-
change reaction to replace the lower alcohols with the higher
. ones. The preferred alcohols are meth~nol, butanol, and similar
lower alkanols with ~ethanol being most preferred.
The preferred aminoplasts are those which are soluble or
sùbstantially h~dratable and dispersible in a~ueous media. Suit-
Iable aminoplasts include those which are substantially miscible in
lU ~all proportions with aqueous alcohol solvent media, such as 5P/50
l-butanol/water mixture. Particularly preferred aminoplasts are
those based on mel~mine, formaldehyde and methanol.
In the preparation of a present invention coating
composition, the aminoplast component is dissolved in an organic
1~ ,solvent to form a solution. To the solution is subsequently added
a selected mixture of polymerizable olefinically unsaturated
monomers and a free radical-generating polymerization catalyst,
and the vinyl polymerization of the monomer mixture is conducted
in the presence of the aminoplast component in a manner which is
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more fully described hereinbelow. The amount of an~inoplast
component will be about 1 to about 12 weight percent, preferably
about 4 to about 8 weight percent, based on total resin component
,!weight, i.e., aminoplast polymerized monomers an~ epoxy resin
'components.
l' Organic Solvent Component
The.organic solvent is preferably one which is substan-
~tially water-miscible, either in the form of a single polar
compound, or as a mixture of compounds which can include non-polar
constituents. The boiling point of the organic solvent component
preferably will vary in the range between about 150F. to about
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Suitable organic solvents, either alone or in admixture,
~include diisobutyl ketone, me_hyl isobutyl ketone, hydroxyethyl
acetate, 2-ethoxyethyl acetate, propylene glycol monomethyl and/or
monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol,
propylene glycol, butylene glycol, diethylene glycol, isopropanol,
~n-butanol, t-butanol, amyl alcohol, cyclohexanol, dioxane, tetra-
~hydrofuran, dimethylformamide, dimethylacetamide, and the li~e.
jNon-polar solvents which can be included as a minor constituent-
iof the organic solvent component include aliphatic and aromatic
hydrocarbons such as naphtha, heptane, hexane, mineral spirits,
~;decane, benzene, chlorobenzene, toluene, xylene, and the like.
¦~ In the preparation of the present invention coating
¦lcomposition, the organic solvent component is employed in a
~quantity between about 30 to about 85 weight percent, preferably
in a quantity between about 40 to about 75 weight percent based
on the total weight of the aminoplast, monomer mixture, epoxy
~resin and organic solvent components present durin~ the preparation
iof the coating composition.
2~ il Polymerizable Monomer Mixture Component
¦l The mixture of monomers employed in the preparation of
a present invention coating composition comprises between about
20 to about 90 weight percent of ~,~-olefinically unsaturated
l~carboxylic acid, and between about 10 to about 80 weight percent
of at least one olefinically unsaturated monomer which is
copolymerizable with the carboxylic acid monomer.
The vinyl polymerization of the monomer mixture yields
,a carboxyl-containing acrylic resin. It is advantageous for
:purposes of the present invention (e.g., for the protective
coating of metal surfaces) to select a mor.omer mixture wlich
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pxovides a carboxyl-containin~ acrylic resin which exhi~its a
Tg (glass transition temperature) in the range between about
;0 to a~out 130C., and preferabl-y a Tg in the range be.ween
. about 50~ to about 90~C. The T~ parameter is that measured for
an acrylic resin obtained by the polymerization of a monomer mix-
ture under the step (2) condition~ of the invention proce~s,
~excluding the presence of the aminoplast components.
i' Suitable ~,~-olefinically unsaturated carboxylic acid
jmonomers include acrylic acid, methacrylic acid, crotonic acid,
itaconic acid (or anhydride), maleic acid (or anhydride), fumaric
acid, the monoesters of the dicarboicylic acid monomers such as
methyl hydro~en maleate, ethyl hydrogell fumarate, and the like.
The one or more other constit~ents of the polymerizable
monomer mixture are alkyl esters o~ ~y~-olefinically unsaturated
carboxylic acids, for example me~.hyl, ethyl, propyl, ~utyl, hexyl,
ethylhexyl and lauryl acrylate, methacrylate and crotonate;
dimethyl maleate; dibutylfumarate and dihexylitacona-te; and
m xtures thereof.
, The polymerizable monomer mixture can also include one or
'more monomers selected from vinyl aromatic compounds. Illustrative~
;of such compounds are styrene, alkyistyrene~, halostyrenes,
-methylst~,rene, isopropenyltoluene, vinylnaphthalene, and the
! like .
Other suitable vinyl polymerization monomer species
include vinyl chloride, acrylonitrile, methacrylonitrile, vinyl
acetate, vinyl propionate, vinyl stearate, acrylamide, methacryl-
,amide, and the like.
The preferred monomers are methylacrylate, ethyl
acrylate znd acrylic acid. The amount of monomers that are
polymerized are that a~.nour.t which ~ill prod~ce a polymer havi.;~ a
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weight percentage in the mixed resin system of about 20 to about
40 w~eigh~ percent, preferably about 25 to about 35 weight percent,
said weight percents being based on the total weight of aminoplast,,
polymerized monomers and epoxy resin components. I
poxy Resin Component
j The epoxy resins useful in this invention are glycidyl
,polyethers of polyhydric phenols and hydrogenated phenols and
,contain more than one 1,2-epoxide group pex molecule. Such
~polyepoxide resins are derived from an epihalohydrin and a poly-
ihydric phenol or hydrogenated phenol and have epoxide equivalent
weights of about 150 to about 8,000. Examples of epihalohydr~ns
jare epichlorohydrin, epibromohydrin and epiiodohydrin with
~epichlorohydrin being preferred. Pol~hydric phenols are exempl.i-
,fied by resorcinol, hydroquinone, p,p'-dihydroxydiphenylpropane
-(or Bisphenol A as it is commonly called), p,p'-dihydroxydiphenyl
ethane, bis(2-hydroxynaphthyl)methane, 1-5-dihy~roxynaphthalene,
novolak resins made from the reaction of mono and diphenols with
aldehydes, phloroglucinol and the like with Bisphenol A being
'preferred. Epoxy resins made from hydrogenated versions of these
Iphenols are also useful in this invention. These epoxy resins ~ I
are well known in the art and are made in desired molecular ¦
,weights by reacting the epichlorohydrin and the polyhydric compound
~in various ratios or by reacting a dihydric phenol with a lower
Imolecular weight epoxy resin. Particularly preferred epoxy resins
llfor use in this invention are glycidyl polyethers of Bisphenol A
. having epoxide equivalent weights of about 1000 to about 4000.
jl In the preparation of the stable aqueous dispersions of
ithis invention, be~ween about 48 to about 79 weight percent,
,preferahly between about 57 to about 71 weight percent, said weight
'percents being based on total weight of aminoplast, polymerized
monomers and epoxy resin components, of a selected epoxy resin are
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adm:ixed and interacted with the product solution resulting from
the previoùsly conducted polv~erization of the monomer mixture
component in the presence of the aminoplast component.
I! SPECIFIC ASPECTS OF DISPERSION PREPAR~TION
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The aminoplast component is admixed with the organic
solvent and heated until the aminoplast is essentially completely
!' dissolved. In some cases, the aminoplast may only partly dissolve
with the undissolved portion remaining dispersed.
Il The organic solvent medium containing the aminoplast is
heated to a temperature in the range between about 120 to about
300~F. To the heatea solvent medium is added the monomer mix*ure
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,component which contains a vinyl polymerization catalyst, i.e.,
a free radical producing catalyst. The catalyst is employed in
;a quantity between about 0,2 to about 14 weight percent, based on
Ithe weight of the monomer mixture. The quantity of catalyst must
be sufficient to promote the cop~lymerization of the monomer con-
j',stituents under the processing conditions. A preferred polymeri-
zation catalyst is an organic peroxide ~?hich is free radical--gen-
erating under the polymerization conditiQ~S, e.g., benzoyl
~0 ,peroxide, tertiary-butyl peroctoate, and the lil~e. Other useful
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jcatalys~ are the aæo catalyst, e.g., azobisisobutyryl nitrile.
The homogeneous blend of polymerization catalyst and
monomer mixture is added slowly to the heated solvent medium at a
liuniform rate. The period of addition can vary in the range
llbetween about 0.5 to about 6 hours, and, on the average, the
¦~addition period will vary in the range between about 1 to about
¦'4 hours.
While not wishing to be bound by any theory or mechanism
lof reaction, there is some evidence that during the course of the
jvinyl polymerization reaction, some interaction occurs bet~een
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~¦one or more of ~he monomer constituents and the aminoplast
component,`and there is some lin~age formed between the aminoplast
and the acrylic copolymer which concomitantly has formed during
the polymerization reaction.
` Upon the completion of the polymerization reaction
period, in a preferred embodiment the resultant polymerization
medium is in the form of a clear homogeneous solution. While
Imaintaining the said product solution at a temperature in the
l'range of about 100 to about 300Or., the epoxy resin component is
~added to the heated solution with the aid of efficient stirring.
The hea~ing and stirring is continued for an additional period
! between about 0.1 to about 2 hours to permit interaction and
~equilihration between the aminoplast and acrylic copolymer an~ i
iepoxy resin components to be complet d. Alternatively, the
Ipolymer solution can be added to the epoxy resin with heating and
stirring as described above.
Depending on the combination of factors involved, the
reaction product medium will vary between being a clear solution
or a solution which exhibits a milky ir~idescence. It i6 highly
j~preferred that the reaction product medium does not contain any
jfilterable solids when it is subjected to the neutralization step
¦of the invention process.
¦ The reaction product medium is trea~ed with a basic
reagent to at least partially neutralize the carboxylic acidity
25 ~which is present. It is essential that the degree of neutraliza- ¦
¦,tion be sufficient to provide a product medium pH which is in the
¦~lrange between about 2 to about 10, and preferably in the range
llbetween about 4 to about 8. The resultant neutralized product
¦imedium normally is in the form of a clear single phase solution.
Besides improving the solubility properties of the resinous
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iconstituents of the product medium, the neutralization step
suppresses the level of functional group interaction and imparts
stability to the product medium.
i As another important aspect of the present invention,
j it is essential that the nuetralized carboxylic acid groups in
the dispersion coating composition be converted to free carboxylic ,
~acid groups during any subsequent heat-curing cycle to which the
~coating composition is sub~ected. In order to satisfy this
I~requirement, it is preferred to employ a basic reagent for the0 `neutralization step which is either ammonia or an organic amine.
Illustrative of suitable basic reagents are primary,
, secondary and tertiary amine compounds, such as ethylamine,
butylamine, dimethylamine, aiisopropylamine, dimetllylethylamine,
Icyclohexylamine, allylamine, benzylamine, m-toluid.ine, mor~holine, ' -
1~ 'ethanolamine, diethanolamine, triethanolamine, and the like, and
other basic reagents such as ammonium hydroxi2e.
~i Having obtained a neutralized product medium ~hich is
nominallS~ a single phase solution containing solubilized mixed
resin solids, the said solution is admixed with an ~queous phase
.20 lland~agitated vigorously to effect a stable aqueous dispersion
~! f thè mixed resin solids in the form of an emulsion. The
average particle size of the dispersed mixed resin solids is
¦preferably less than one micron.
i! An aqueous dispersion of mi~ed resins p_oduced in
accordance with the present invention process inherently has
lexceptional phase stability and shelf-life. A typical aqueous
dispersion coating composition of the present inv~ntion can
remain substantially unchanged for more than one year at 77F.
lAn invention aqueous dispersion coa~ing comPositi~n is capable
of tolerating a 120F. temperature for more than three months
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¦Iwithout any apparent visible change in the dispersion phases.
The quantity of water employed for the dispersion-forming
procedure can vary over a broad range as dictated by practical
, considerations. A typical aqueous dispersion will have a solids
~,content in the range between about 15 to about 40 weight percent,
and preferably in the range between about 20 to about 30 weight
~percent, based on the total weight of the aqueous dispersion.
Optionally there can be incorporated into the invention
. ~aqueous dispersion coating composition other componènts which do
l'not interfere with the stability and other advantageous properties
of the coating composition. Illustrative o~ an additional
,component which may be employed is between about 0.05-5 weight
percent of a plasticizer, based on the weight of the resinous
Ijfilm-forming solids in a coating composition. Typical plasticizers
j include butyl benzyl phthalate, dibutyl phthalate, triphenyl
phosphate, dicyclohexyl phthalate, dibenzyl phthalate, mixed
l benzoic acid and fatty oil acid esters of pentaerythritol,
¦,diethyleneglycol dibenzoate, butyl phthalyl butyl glycolate,
lltricresyl phosphate, toluene ethyl sulfonamide, hexamethylene
? i diphthalate, and the like. Additional other components are
~Icolorants, waxes and the like.
l! As noted previously during the baking and curing phase
the volatile basic reagent employed to neutralize the coating
Icomposition evolves from the applied coating~ thereby providing
!Ifree reactive carboxyl groups. The said reactive carboxyl groups
!linteract with the epoxy groups of the epoxy component to yield
j crosslinked ester linkages. Hydroxyl groups which are initially
present and which are formed in situ during the baking cycle are
! highly reactive and condense with the aminoplast component, thereby
I providing an additional crosslinking mechanism.
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¦~ The coating compositions of this invention are particu-
larly useful as coating compositions for the interior of aluminum
and steel cans and can be applied to the interior of said cans by
.airless spray application. The closures of such cans can also be
S jcoated with the compositions of this invention, such coatings
jbeing applied by roller coating processes. The coatings for cans
`are applied to dry film thicknesses of 0.1 to 0.5 mil and are
i~cured by passing the metal through gas fired ovens heated to 315
i!to 425F. in stages. The total residence time in these ovens is
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I~a matter of seconds, 30 seconds to 4 minutes.
i' In other applications, i.e., as metal primer coatings,
~the coating compositions are cured at a temperature of about
~300F. to about 500F. for a time sufficient to obtain a cure.
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jThe coating compositions can be formulated into clear coatinqs as
hereinbefore described or into pigmented coatings. Pigments can
be added using well known formulating procedures. Other additi~-es
-which can be incorporated in the coating compositions are coales-
cing sol~ents, leveling a~ents, wettin~ agents, dispersions of
;other resins, water soluble resins,-thickening agents, suspending
~20 agents, suractants, defoamers, adhesion promoters, and the like.
The following examples are presented to more clearly
define the invention. Parts and percentages unless othen~ise 3
designated are parts and percentages by weight. .
IlI EXP~;PLE 1
i To a suitable reactor equipped with a stirrer, tempera-
''ture recording device, reflux condenser and dropping fur.nel were
~added 6Q parts of hexamethoxymethyl melamine (Cymel*300 available
from American Cyanamid Co.), 220 parts of ethylene glycol monobutyl
lether and 406 parts of n-butanol. To the droppin~ funnel were
added 128 parts of metnacrylic acid, 80 parts of styrene, 88 parts
,of ethyl acrylate and 40 parts of a 50/50 blend of benzovl
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peroxiue and tricresyl phosphate. Heat and stirring were applied
raising the reactor contents to ~5C. At this temperature, the
slow addition of the monomer-catalyst sol~tion from the dropping
:, !
funnel was begun. The addition was completed after 90 minutes
with the temperature rising to 104C. The temperature was held
at 104-10?C. for 90 minutes to complete the polymerization
;reaction. 696 parts of pulverized glycidyl polyether of Bisphenol
'A having an epoxide equivalent weight of 2700 and a melting point
l~of about 150C. were then added. ~leating and stirring were
continued until the glycidyl polyether W25 dissolved, a period of
about 45 minutes. N,N-dimethylaminoethanol, 114 parts, was then
added. After 25 minutes and with the temperature at 96C., lnO0
~parts of deionized water were added. Ten minutes later, 1750
parts of deionized water were added. When thoroughly mixed, the , -
emulsion product was cooled and stored in appropriate containers.
'The stable emulsion product had a Brookfield viscosity of 22.5 cps.
,at 25~C. (a 2ahn 2 viscosity of 19 seconds,) a solids content of
23.02%, a weight per gallon (wt/gal) of 8.54 lbs. and a pH of 8.15.
After 3 weeks at room temperature, the composition gelled.
'j The insides of 12 ounce aluminum and electxolytic tin
,jplated (ETP) steel cans were coated with the coating compositionusing airless spray, to a dry film weight of 115 to 125 mg. per can,
(beer weight). The coatings were cured by baking for 60 seconds
lat a peak metal temperature of 1~8C. The continuity of the
lcoatings was determined by a conductivity test carried out by
. filling the coated can with a 10~ solution of sodium chloride in
water and then determining the milliamperes of leakage current
through the coating 30 seconds after a potential of 12 volts is
"applied between the salt solution and the can exterior. High
readings indicate defects ir. the coafing, e.g., craters, voids,
, ~ - 17 -
S ~ ~3 ~
I ~ . .,
`bubbles, etc., which in use could result in contamination of the
can contents and/or corrosion of the container. A milliamp reading
(also re~erred to as Enamel Rater reading) of 0 to 25 is acceptable.
The conductivity of the coatings was found to vary from 0-20
milliamps (ma) with an average, based on 24 cans, of 6.2 ma. When
applied at beverage weights, i.e., 175 to 185 mg. per can, the
milliamp reading was 0 for 24 cans.
~' The blister threshold, i.e., the applied dry film
`,~eight at which blisters or bubbles form in the film from escaping
i~solvent or water, was greater than 180 mg.
Films were cast from the coating composition onto
electrolytic tin ~lated (ETP) steel panels to a dry film thickness
of 0.2 mil using a wire wound Meyer rod. After baking at 188~C.
for one minute, the films-were well cured. After 10 minutes
immersion in a water bath heated to 82~C., the film exhibited no
blushing and passed the wet adhesion test with a rating of 10.
The wet adhesion test was conducted as follows: within one minute
of removal from the water bath described above, ~he film surface
was dried with a cloth and scribed with a cross-hatch pattern. A
high tack cellophane tape was applied over the scribed po~tion and
was removed with a jerk. The amount of film which remained on the
panel was visually estimated and was rated as 10 for no removal
;and 0 for total removal.
! The double coat adhesion was tested by applying a second
2S 'coating over the first cured coating using the same film weight
. and curing conditions as used for the first coating. The wet
adhesion was rated as 7-8.
In all of the following exam~les the wet adhesion as
described above of single coatings was excellent. The a~hesion
3C tests reported in these examples pertain to double coa~ed panels
and cans.
- 18 -
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~1~5484 , i
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EX~MPLE 2
Using the same procedure described in Example 1, 60 parts
of heY~methoxymethyl melamine (Cymel 303 available from American
- Cyanamid Co.) were dissolved in 228 parts of ethylene glycol mono-
butyl ether and 342 parts of n-butanol. To this solution heated
,: ,
'to 93C., was added over a 90 minute period a mixture of 128 parts
if methacrylic acid, 80 parts of styrene, 88 parts of ethyl
acrylate and 40 parts of a 50/50 blend of benzoyl peroxide and
tricresyl phosphate. ~fter holding at 93C. for 3 hours to com-
plete the pol~erization, 696 parts of pulverized glyci~yl
polye~her described in Exa~ple 1 were added. ~fter one hour with
the temperature at 93C., the glycidyl polyether had dissolved.
N,N-dimethylaminoethanol, 57 parts, was added followed by 4~ par~s
'of triethylamine. After holding at 95 to 112C. for 30 minutes,
lS 3186 parts of deionized water w~re added over a 15 minute period.
h'hen thoroughly mixed, the resulting emulsion was cooled and stored
i`n an appropriate container. The emulsion product had a solids
content of 21.96%, a wt/gal. of 8.57 lbs., a pH of 7.7, an acid
value of 49.8 and a Zahn 2 viscosity at 25C. of 23 seconds. The
20product exhibited no instability aftex 2 months at room temperatur~
~100F. and 120F.
The interiors of 12 ounce aluminum and ETP steel cans were
coated, cured and tested using the procedure described in Exa~ple
j'l. The Enamel Rating at beer weights was 44.5 ma. and at beverage
25Iwelghts, 4.6 ma. The blister threshold was less than 170 mg.
I The wet adhesion of coatings on aluminum panels, double
¦coated and cured as described in Example 1, was 7-8 and on ETP
steel panels the wet adhesion was 4-6. The solvent resistance
of the cured coating was determined by rubbing the coating with
30~ethylethyl ketone (MEK). The coating passed 21 double rubs.
. - 19 -
ll ~
I ' ~S~84 .:
` EXAMPLE 3
Usin~ the same procedure as ~escribed in Example 1,
monomer-catalyst solution of 128 parts of methacrylic acid, 80
, parts of styrene, 88 parts of ethyl acrylate and 36 parts of
; t-butyl peroctoate was polymerized in a solution of 60 parts of
i~ ' ' i
ihexamethoxymethyl melamine (Cymel 303), 228 parts of ethylene
liglycol monobutyl ether and 324 parts of n-butanol. When the poly-
merization was completed, 696 parts of the glycidyl polyether
ildescribed in Example 1 were added and dissolved in the reaction
!¦mixture, followed by 114 parts of N,N-dimethylaminoethanol and
¦Ithen by 3204 parts of deionized water. The resulting stable
emulsion had a solids content of 21.85%, a wt/gal of 8.54 lbs., a
pH of 7 9 and an acid value of 46.25. The product was still
llstable after 3 months at room temperature, 100F. and 120F. ¦ .
15 ll The solids were adjusted with water to 19% and the
viscosity to 19 seconds (Zahn 2.at 25C.). The interiors of 12
,ounce aluminum ETP steel cans were coated, cured and tested using
,the procedure described in Example 1. The Enamel Rating at beer
Iweights was 10.2 ma. and at beverage weights, 2.4 ma. The blister
,threshold was 155 mg.
I The wet adhesion of coatings on aluminum and ETP steel
¦panels, double coated and cured as described in Exampie 1, was
~poor. The double coat wet adhesion of the coatings on the
linteriox of aluminum cans was also poor, but on ETP steel cans, thej
~cured coat adhesion was perfect. The solvent resistance of the
. Icured coatings was 100 MEK double rubs.
EXAMPLE 4
Using the same procedure described in Example 1, a
imonomer-catalyst solution of 128 parts of methacrylic acid, 80
;parts of styrene, 88 parts of ethyl acrylate and 20 parts of
Il .
1! 20 -
I' ~ i
! 1 6 5 4 8 4
benzoyl peroxide was polymerized in a solution of 68 parts of
C~nel 370 available from American Cyanamid Co. (hexamethoxymethyl
melamine at 88~ solids in isopropanol), 228 parts of ethylene
llglycol monobutyl ether and 334 parts of n-butanol. When the poly-
jmerization reaction was completed, 696 parts of pulverized glycidyl
polyether described in Example 1 were added followed by 114 parts
of N,N-dimethylaminoethanol and 3204 parts of deionized water.
The resulting stable emulsion had a solids content of 22.18%, a
iwt/gal. of 8.59 lbs., a pH of 7.6 and an acid value of 52.6. The
iproduct was stable after ~ months at room temperature, 100F. and
120F.
The interiors of 12 ounce aluminum and ETP steel cans
were coated, cured and tested using the procedure described in
IlExample 1. The Enamel Rating at beer weights was 10.3 ma. and at
Ibeverage weights, 1.1 ma. The blister threshold was 145-150 mg.
The wet adhesion of coatings on aluminum and ETP steel
panels, double coated and cured as described in Example 1, was
~poor. The double coat wet adhesion of the coatings on the interior
of aluminum cans was also poor, but on ETP steel cans, the double
~0 !coat adhesion was perfect. The cured coatings passed 50 MEK
¦double rubs.
¦ ` EX~MPLE 5
¦ Using the same procedure described in Example 1, a
Imonomex-catalyst solution of 137 parts of methacrylic acid,
1l86 parts of styrene, 94 parts of ethyl acrylate and 22 parts of
benzoyl peroxide was polymerized in a solution of 280 parts of
Ihexamethoxymethylamine (Cymel 303) in 220 parts of ethylene
¦glycol monobutyl ether and 330 parts of n-butanol. When the
¦polymerization reaction was completed, 645 parts of the glycidyl
Ipolyether described in Example 1 were added, followed by 123 parts ;
of N,N-dimethylaminoethanol and 3147 parts of deionized water.
- 21 -
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,` Il` , `
548~ ~
The resulting stable emulsion had a solids content of 24.34~,
a wt/gal. of 8.61 lbs., a pH of 7.7 and an acid value of 47.2.
The ~ispersions were still stable after 3 months at xoom tempera-
tu.e and at 100F., but had settled out at 120F.
, The solids and viscosity (Zahn 2 at 25C.) were adjusted
to 22~ and 30 seconds respectively with water.
The interiors of 12 ounce aluminum and ETP steel cans
were coated, cured and tested using the procedure described in
Example 1. ~he Enamel Rating at beer weights was 2.3 ma., and
~ at beverage weights, 1.5 ma. The blister threshold was 135 mg~
!i ` The wet adhesion of double coatings on aluminum and
ETP steel panels and on ETP steel cans was poor. The wet adhesion,
however~ on aluminum cans had a rating of 7-8. The solvent
; resistance of the cured coatings was 28 MEK double rubs.
1I EXAMPLE 6
!~ Using the same procedure described in Example 1, a
monomer catalyst solution of 137 parts of methacrylic acid, 87
parts of styrene, 95 parts of ethyl acrylate and 22 parts o~
~ benzoyl peroxide was polymerized in a solution of 19 parts of
I'hexamethoxymethyl melamine (Cymel 303) and 28 parts of hexabutoxy-
methyl melamine in 220 parts of ethylene glycol monobutyl ether
lland 330 par*s of n-butanol. When the polymerization reaction was
;~completed, 793 parts of the glycidyl polyether described in
',Example 1 were added followed by 123 parts of N,N-dimethylamino-
',ethanol and 3150 parts of deionized water. The resulting stable
emulsion had a solids content of 24.44, a wt/gal. of 8.62 lbs. and
',an acid value of 46.6. T}le dispersion was stable after 3 months at
room temperature, but exl~ibited slight settling after 3 months at
lOO~F. and comple~e instability at 120F.
The interiors of 12 ounce aluminum and ETP steel cans
. - 22 -
; .
16548~ . I
were coa~ed, cured and tested using the procedures described in
Example 1. The Enamel Rating at beer weight~ and at beverage
weights was 7.7 ma. The blister threshold was 135 mg.
Il The wet adhesion o~ double coatings on both aluminum
S and ETP steel panels and cans was poor. The solvent resistance
of the cured coatings was 50 MEK double rubs.
EXAMPLE 7
i To a suitable reactor equipped as described in ~xample 1
~were added 280 parts of n-butanol and 280 parts of ethylene glycol
~monobutyl ether. To ~he dropping funnel were added 129 parts of
~methacrylic acid, 131 parts of styrene, 197 parts of ethyl acrylate
tand 24 parts of benzoyl peroxide. ~eating and stirring were begun
and at 93C., the addition of the monomer-catalyst solution was
,~begun. After 90 minutes, all o the monomer-catalyst solution had
been added and heating at 93-95C. was continued for 3 hours.
After this heating period, 624 parts of pulverized glycidyl poly-
ether of Bisphenol A having an epoxide equivalent weight of 1850
and a melting point of about 130C. were added. Heating and stir-
jring were continued and after 1 hour and 25 minutes at 108C.,
114 parts of N,N-dimethylaminoethanol were added followed 30
minutes later by 96 parts of hexametho~ymethyl melamine (Cymel
~303). Heating was discontinued and at 88C., 3128 parts of
~deionized water were added. The resulting dispersion after
¦cooling had a solids content of 24.3%, a wt/gal. of 8.59 lbs., a
~5 iipB of 7.7 and an acid value of 51Ø The dispersion was not
stable. It completely settled out after 2 weeks at room
jitemperature, 100F. and 120F.
¦i The interiors of aluminum and ETP steel cans were spray
coated, cured and tested as described in Example 1. The material
was foamy and had poor atomization. The Enamel Ratin~ at becr
j - 23
.,
!;
., .
! 165~18'~
¦wei~hts and at beverage weights was 9.3 and 4.4 ma. respectively.
The blister threshold was 155 mg.
, The wet adhesion on aluminum and EPT steel panels was
excellent. The wet adhesion on aluminum cans was poor but on ETP
steel cans, it was almost perfect. The solvent resistance of the
cured coatings was 18 ~X double rubs.
~; EXAMPLE 8
il Using the same procedure described in Example 1, 4.2
~pàrts of methacrylic acid, 2.8 parts of styrene and 3.11 parts of
'ethyl acrylate were copolymerized with 0.65 part of benæoyl
peroxide in a solution of. 2.16 parts of hexamethoxymethyl melamine
(Cymel 303), 6.54 parts of ethylene glycol monobutyl ether and
.8 parts of n-butanol. ~hen the polymerization was completed,
~3.04 parts of pulverized glycidyl polyether of Bisphenol A as
described in Example 1 were added and dissolved. N,N-dimethyl-
aminoethanol, 3.7 parts, was added followed by ~3.8 parts of
,
deionized water. The resulting dispersion had a solids content of
24.08%, a wt/gal. of 8.62 lbs., a pH of 7.7 and an acid value of
;59.9.
, . . .
2Q , The solids and viscosity ~Zahn 2 at 25C.) were adjusted `
with wa~er to 23~ and 24", respectively. The interiors of
aluminum and ETP steel cans wère spray coated, cured and tested as
described in Example 1. The Enamel Rating at beer and beverage
lweights was 14.2 and 1.3 ma., respectively. The blister threshold
Iwas 210 mg.
Il The wet adhesion on aluminum panels was good, a 7-8
"rating, but was poor on ETP steel panels. The wet adhesion on
aluminum and ETP steel cans was poor. Solvent resistance was
16 MEK double rubs.
1 ;
- 24 -
!
. . ~
4 8 ~ . ¦
EXAMPLE 9
; ~sing the same procedure described in Example 1, a
monomer-catalyst solution of 140 parts of methacrylic acid, 122
parts of styrene, 133 parts of ethyl acrylate and 25 parts of
benz:oyl peroxide was polymerized in a solution of 72 parts of
hexamethoxymethyl melamine (Cymel 303) in 326 parts of n~butanol
"and 218 parts of ethylene glycol monobutyl ether. When the poly-
merization reaction was complete, 708 parts of the glycidyl
ipolyether described in Example 1 were added followed by 123 parts
'of N,N-dimethylaminoethanol and 3132 parts of deionized water.
The resulting stable emulsion had a solids content of 24.21~, a
~wt/gal. of 8.61, a pH of 7.8 and an acid value of 54.5. The
stability was excellent after 3 months at room temperature and
lOO~F. with slight settling at 120~F.
The solids and viscosi.ty (Zahn 2 at 25C.) were adjusted
with water to 23.2g and 25 seconds respectively. The interiors of
, aluminum and ETP steel cans were spray coated, cured and tested as
described in EY.ample 1. The Enamel Rating at beer and beverage
jweights was 20.9 and 5.8 ma., respectively. The blister threshold
was 135 mg.
The wet adhesion on aluminum panels was excellent but
~ poor`on ETP steel panels. The wet adhesion on aluminum can
i interiors was poor and was just slightly better on the interiors
i'f ETP steel cans. Solvent resistance of the cured coatinys was
~ 19 MEK double rubs.
EXAMPLE 10
Using the same procedure described in Example 1, a `
monomer-catalyst solution of 100.1 parts of acrylic acid, 91
, parts of methyl acrylate, 91 parts of ethyl acrylate an~ 23.2
parts of a catalyst biend of 78% be~zoyl peroxide and 22% water
- 25 -
¦wa~ polymerized in a solution o~ 72 parts of llexamethoxymethyl
melamlne (Cymel 303) in 408.5 parts of n-butanol and 273 parts of
ethylene glycol monobutyl ether. When the polymerization reaction
was completed, 828 parts of the glycidyl polyether descri~ed in
Example 1 were added followed by 111.4 parts of N,N-dimethylamino-
ethanol and 3001.1 parts of deionized water. The resulting stable ;
emulsion had a solids content of 24.63%, a wt/gal. ~f 8 . 6 lbs. and
~'a pH of 7Ø After 2 months at room temperature, 100F. and 120F.,
,'the dispersion exhibited medium to large settling which could be
~stirred back in.
The interiors of aluminum and ETP steel cans were sp~ay
coated, cured and tested as described in Example 1. The Enamel
Ratings at beer and beverage weights was 0.1 and 0.04 ma.,
.
~respectively~ The blister threshold was 245-250 mg.
I The wet adhesion on aluminum panels and on the interior
of aluminum and ETP steel cans was perfect. The wet adhesion on
ETP steel panels was almost perfect. The solvent resistance was
4 ~EK double rubs.
~ EXAMPLE 11
j Using the same procedure described in Example 1, 2
~monomer-catalyst solution of 115.5 parts of acrylic acid, 88.1
Iparts of methyl methacrylate, 22.0 parts of 2-ethylhexyl acrylate
'Ian~ 18.5 parts of a blend of 78% benzoyl peroxide and 22% water
~were polymerized in a solution of 72 parts of hexamethoxymethyl
~melamine (Cymel 303) in 424.9 parts of n-butanol and 283.3 parts
of ethylene glycol monobutyl ether. When the pol~merization
reaction was completed, 888 parts of the glycidyl polyether
~described in Example 1 were added followed by 85.7 parts of
,N.N-dimethylaminoethanol and 3002 parts of deionized water. The
resulting stable dispersion had a solids content of 25.4%, a
,: ;
- 26 -
. ~ i ' 1 ~ 4
wt~gal.~of 8.6 lbs. and a p~ of 6.67. The dispersion exhibited
no instability after 3 months at room temperaturer 100F. and
120F.
The interior of aluminum and ETP steel cans were spray
Icoated, cured and tested as described in Example 1. The Enamel
,Rating at beer and beverage weights was 5.8 and 0.4 ma.,
respectively, The blister threshold was 160 mg.
The wet adhesion on aluminum panels was almost perfect
(9-10) and on ETP steel panels, it was 7-8. The wet adhesion of
'coatings on the interior of aluminum cans was perfect (lO) and on
ETP steel cans almost perfect (9-10). The solvent resistance was
l13 MEK double rubs.
i EXAMPLE 12
~ Using the same procedure described in Example 1, a
llmonomer-catalyst solution of 115.5 parts of acrylic acid, 90
¦~parts of methyl methacrylate, 22.5 parts of 2-ethylhexyl acrylate
¦and 15.4 parts of a blend of 78~ benzoyl peroxide and 22% water
was polymerized in a solution of 72 parts of hexamethoxymethyl
imelamine (Cymel 303) in 433.5 parts o~ n-butanol and 289 parts
,of ethylene glycol monobutyl ether. When the polymerization
~reaction was completed, 888 parts of the glycidyl polyether
described in Example 1 were added, followed by 71.4 parts of
¦N,N-dimethylaminoethanol and 3006.2 parts of deionized water.
. IThe resulting stable dispersion had a solids content of 24,83%, a
iwt/gal. of 8.56 lbs. and a p~ of 6.1. The dispersion exhibited
soft settling after 3 months at room temperature, 100F. and
120F.
Using the procedure described in Example 1, the interior
of aluminum and ETP steel cans were spray coated, cured and tested.
30 ¦jThe Enamel Rating at beer and beverage weights was 1.5 and Q.8 ma.
I! .
~ 27 -
'` I 1165~134
respectively. The blister threshold was 200 mg.
The wet adhesion on the interior of aluminum and ETP
steel cans was perfect (10), on aluminum panels almost perfect
~(9--10) and on ETP steel panels 4-6. The solvent resistance was
S ~lS MEK double rubs.
¦ EXAMPLE 13
Using the same procedure described in Example 1, a
Imonomer-catalyst solution of 112.6 parts of acrylic acid, 102.3
jparts of methyl acrylate, 102.3 parts of ethyl acrylate and 26
parts of a blend of 78% benzoyl peroxide and 22% water was
;polymerized in a solution of 81 parts of hexamethoxymethyl
melamine (Cymel 303) in 461.3 parts of n-butanol and 307.5 parts
f ethy~ene glycol monobutyl ether. When the polymerization
reaction was completed, 931.5 parts of the glycidyl polyether
lS jdescribed in Example 1 were added followed by 139.2 parts of
N,N-dimethylaminoethanol and 2737.3 parts of dei~nized water. The
¦~resulting stable dispersion had a solids content of 28.0%, a
wt/gal. of 8.62 lbs. and a pH of 7.95. The dispersion exhibited
jisoft settling after 3 months at room temperature, 100F. and
,120F.
The solids and viscosity (2ahn 2 at 25C.) were adjusted
!wit~ water to 26.8% and 21 seconds respectively. The interior
¦of 12 ounce aluminum and ETP steel cans were spray coated using the
. Iprocedure described in Example 1. The Enamel Rating at beer and
llbeverage weights was 0.4 and 0 ma. respectively. The blister
¦'ithreshold was 230-235 mg.
¦ The wet adhesion on aluminum and ETP steel panel and can `
¦!interiors was perfect. The solvent resistance was50MEK double
!rubs. ''
30 1i
1 - 28 -
.
,
I 11654~d
EXAMPLE 14
Using the same procedure described in Example 1, a
monomer-catalyst solution of 403.6 parts of acrylic acid, 366.6
~ parts of methyl acrylate, 366.6 parts of ethy~ acrylate and 93.2
parts of a catalyst blelld of 78~ benzoyl peroxide and 22% water
I was polymerized in a solution of 290.3 parts of hexamethoxymethyl
melamine (Cymel 303) in 887~8 parts of n~butanol and 591.7 parts
' of ethylene glycol monobutyl ether.
! To another reactor were added 165.2 parts of the
diglycidyl ether of Bisphenol A having an epoxide equivalent
weight of 190 and 83.2 parts of Bisphenol A. Heat was applied
i raising the temperature to 121C. Potassium hydroxide, 0.042
part of a 45~ aqueous solution, was added, and heating was
, continued raising the temperature to 177C. Heating was discon-
' tinued and the temperature was allowed to rise to 204C. due to
the exothermic reaction. The temperature was then held at 204C.
for 3 hours and 45 minutes. Heating was discontinued and 69.9
parts ethylene glycol monobutyl ether were added over a five
minute period with the temperature dropping to 177C. N-butyl i
alcohol 104.7 parts was then added with the temperature dropping
to 131C. The temperature was then lowered to 99C. and 223.2
, parts oE the hexamethoxymethyl melamine/polymer solution,
! described in the first paragraph of this example, were added o~er.,
I a 5 minute period with the temperature dropping to 82C. The
25Itemperature was raised to 93C. and was held at 93C. for 45
minutes. Dimethylethanol amine, 15.8 parts, and triethylamine,
17.9 parts were then added. The temperature was held at 93-96C. i
for 15 minutes~ Deionized water, 1500 parts, was then added over
la 10 minute period. The reaction product was cooled to 38C.,
30was fi~tered and stored. The resulting product was a stable
!
' I .
ll
~ 1~54~ '
dispersion having a solids content of 24.34~. Coatings on steel
and aluminum cans, prepared as described in the preceding examples,!
exhibited excellent coating properties. I
.. !
The principles, preferred embodiments and modes of
operation of the present invention have been described in the
!~foregoing specification. The invention which is intended to be
jprotected herein, however, is not to be construed as limited to
the particular forms disclosed, since these are to be regarded
~ as illustrative rather than restrictive. Variations and changes
may be made by those skilled in the art without departing from
the spirit of the invention.
!
,~ ,
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20 11 .
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i,l I
i
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